Campus Units

Biochemistry, Biophysics and Molecular Biology

Document Type

Article

Publication Version

Accepted Manuscript

Publication Date

2012

Journal or Book Title

Natural Product Reports

Volume

29

Issue

10

First Page

1153

Last Page

1175

DOI

10.1039/C2NP20059G

Abstract

The complexity of terpenoid natural products has drawn significant interest, particularly since their common (poly)isoprenyl origins were discovered. Notably, much of this complexity is derived from the highly variable cyclized and/or rearranged nature of the observed hydrocarbon skeletal structures. Indeed, at least in some cases it is difficult to immediately recognize their derivation from poly-isoprenyl precursors. Nevertheless, these diverse structures are formed by sequential elongation to acyclic precursors, most often with subsequent cyclization and/or rearrangement. Strikingly, the reactions used to assemble and diversify terpenoid backbones share a common carbocationic driven mechanism, although the means by which the initial carbocation is generated does vary. High-resolution crystal structures have been obtained for at least representative examples from each of the various types of enzymes involved in producing terpenoid hydrocarbon backbones. However, while this has certainly led to some insights into the enzymatic structure–function relationships underlying the elongation and simpler cyclization reactions, our understanding of the more complex cyclization and/or rearrangement reactions remains limited. Accordingly, selected examples are discussed here to demonstrate our current understanding, its limits, and potential ways forward.

Comments

This is a manuscript of an article published as Gao, Y., Honzatko, R.B., Peters, R.J. (2012) “Terpenoid synthase structures: a so far incomplete view of complex catalysis”, Nat. Prod. Rep., 29(10):1153-1175, doi: 10.1039/C2NP20059G. Posted with permission.

Copyright Owner

The Royal Society of Chemistry

Language

en

File Format

application/pdf

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